Patent GB-368509-A (GB)
Title: Improvements in and relating to the manufacture of rubber
IPC: C08K5/00
Filed: 1931-02-26
Abstract: Dithiocarbamates.--Vulcanization accelerators comprise dithiocarbamates of quaternary ammoniums of the general formula:-- <FORM:0368509/IV/1> wherein R1, R2 are the same or different monovalent organic radicles, at least one of which is alkyl, for example methyl, ethyl, or propyl; thus they may represent aryl, aralkyl, or an alicyclic radicle such as cyclohexyl, or together a single divalent radicle such as a polymethylenic chain (piperidyl): R3, R4 are the same or different monovalent organic radicles or together represent a single divalent radicle similar or not to those of R1, R2: R is hydrogen or an aliphatic radicle.  These products may be prepared by condensation of aliphatic aldehydes with disubstituted dithiocarbamates of disubstituted quaternary ammoniums.  Thus by condensing formaldehyde with the appropriate disubstituted dithiocarbamate of disubstituted ammonium, methylenedimethylammonium - dimethyldithiocarbamate, methylenepiperidylammonium-piperidyldithiocarbamate, and methyleneethylcyclohexylammonium - ethylcyclohexyldithiocarbamate are obtained.  Similar derivatives are obtained by using acetaldehyde and other aliphatic aldehydes.  When derivatives are desired in which one of the positions R3, R4 is occupied by an aromatic radicle, the condensation is modified and the disubstituted dithiocarbamate of ammonium itself is condensed with an aldehyde. Thus according to examples (1), piperidylammonium-piperidyldithiocarbamate is added to 40 per cent formaldehyde to give methylenepiperidylammonium-piperidyldithiocarbamate and (2) ammonium-methylphenyldithiocarbamate is added to acetaldehyde to give ethylidenemethylphenylammonium-methylphenyldithiocarbamate.ALSO:Vulcan ization accelerators comprise dithiocarbamates of quaternary ammoniums of the general formula- <FORM:0368509/V/1> wherein R1, R2 are the same or different monovalent organic radicles, at least one of which is alkyl, for example, methyl, ethyl or propyl; thus they may represent aryl, aralkyl, or an alicyclic radicle such as cyclohexyl, or together a single divalent radicle such as a polymethylenic chain (piperidyl): R3 and R4 are the same or different monovalent organic radicles or together represent a single divalent radicle similar or not to those of R1 and R2: R is hydrogen or an aliphatic radicle.  These products may be prepared by condensation of aliphatic aldehydes with disubstituted dithiocarbamates of disubstituted quaternary ammoniums.  Thus by condensing formaldehyde with dimethylammonium-dimethyldithiocarbamate, piperidylammonium-piperidyldithiocarbamate, ethylcyclohexylammonium-ethylcyclohexyldithiocarbamate, the corresponding methyleneammonium derivatives of these compounds are obtained.  When derivatives are desired in which one of the positions R3, R4 is occupied by an aromatic radicle, the condensation is modified and the disubstituted dithiocarbamate of ammonium itself is condensed with an aldehyde.  Thus according to examples (1) piperidylammonium-piperidyldithiocarbamate is added to formaldehyde to give methylenepiperidylammonium - piperidyldithiocarbamate; (2) ammonium - methylphenyldithiocarbamate is added to an excess of acetaldehyde to give ethylidenemethylphenylammonium-methylphenyldithiocarbamate. Other aliphatic aldehydes may be used with similar results. These accelerators are free from the disadvantages of preliminary "scorching" associated with the parent materials and they may also act as true antiagers.